WO2012010515A1 - Plastiques perfluorés modifiés, leur procédé de fabrication et leur utilisation - Google Patents

Plastiques perfluorés modifiés, leur procédé de fabrication et leur utilisation Download PDF

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Publication number
WO2012010515A1
WO2012010515A1 PCT/EP2011/062150 EP2011062150W WO2012010515A1 WO 2012010515 A1 WO2012010515 A1 WO 2012010515A1 EP 2011062150 W EP2011062150 W EP 2011062150W WO 2012010515 A1 WO2012010515 A1 WO 2012010515A1
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modified
ptfe
groups
chemically
perfluoropolymers
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PCT/EP2011/062150
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German (de)
English (en)
Inventor
Dieter Lehmann
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Leibniz-Institut Für Polymerforschung Dresden E.V.
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Priority to EP11746496.6A priority Critical patent/EP2596029B1/fr
Publication of WO2012010515A1 publication Critical patent/WO2012010515A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/28—Treatment by wave energy or particle radiation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/22—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols

Definitions

  • the invention relates to the field of chemistry and relates to modified perfluoroplastics, for example, as additives for oils and fats or as bonded coatings, equipped with special adhesive / coupling groups, which are suitable for fixing to substrate surfaces, such.
  • Metal surfaces serve, can be used, and a method for their preparation and use.
  • PTFE unlike its high chemical and thermal stability, is extremely radiation sensitive. It is degraded both under inert conditions and in the presence of oxygen even at low energy dose, even at 0.2 to 0.3 kGy brittle and ⁇ 100 kGy friable. ... From about 360 ° C, the purely radiation-chemical degradation is noticeably superimposed by a thermal. ...
  • peroxy- and alkoxy radicals are formed from the initially formed perfluoroalkyl radicals.
  • the terminal perfluoroalkyl radical is gradually degraded by chain shortening and formation of carbonyl difluoride ...
  • perfluoroalkanoic acid fluorides and terminal perfluoroalkyl radicals are formed from the pendent alkoxy radicals.
  • Perfluorinated diacids are also formed in very small quantities, as two lateral radical centers can be formed on a perfluorocarbon chain ... ...
  • Unsintered and unspiked PTFE emulsion and suspension polymers are of a fibrous-felty character.
  • a transmission z As the anti-adhesive and sliding properties of PTFE to other media by incorporation into aqueous or organic dispersions, polymers, paints, varnishes, resins or lubricants is not possible because this PTFE can not be homogenized, but tends to clumping, agglomerated, floating or itself settles.
  • a free-flowing fine powder is obtained from the fibrous-felted polymers as a result of partial degradation of the polymer chains.
  • This powder still contains loose agglomerates, which can easily be divided into primary particles with a particle diameter of less than 5 ⁇ m.
  • functional groups are incorporated into the polymer. If the irradiation takes place in air, then according to Eq. (9.22) (and subsequent hydrolysis of the -COF groups by atmospheric moisture) obtained carboxyl groups. If 2 S0 3 is added before the irradiation (NH 4 ), then S-containing groups can be obtained.
  • the utilization of the products of the PTFE degradation takes place in a variety of applications - as well as an additive to plastics for the purpose of achieving sliding or non-stick properties.
  • the fine powder substances are more or less finely dispersed as a filler component in a matrix [Ferse et al., Plaste u. Kautschuk, 29 (1982), 458; Ferse et al. DD-PS 146 716 (1979)].
  • the matrix component When dissolving the matrix component, the PTFE fine powder is eliminated or recovered.
  • grafted fluorine-containing plastics which consist of fluorine-containing plastic particles, on the surface of which a non-homopolymerized ethylenically unsaturated compound is grafted.
  • the non-homopolymerized ethylenically unsaturated compounds may be acids, esters or anhydrides.
  • These grafted fluorine-containing plastics are prepared by subjecting the fluorochemical polymer powder produced by the melt process to a source of ionizing radiation in the presence of the ethylenically unsaturated compound is suspended. In this case, the attachment of the ethylenically unsaturated compounds to the surface of the fluorine-containing plastic particles takes place.
  • the PTFE is physically intercalated in technical composites and more or less uniformly distributed.
  • the embedded PTFE forms imperfections in the material system, which lowers the interlaminar bond strength.
  • modified perfluoro-plastics consisting of under oxygen influence Strahlenchem isch or plasmachem isch modified perfluoropolymers, which simultaneously contain free radicals and -COOH and / or -COF- groups, to the further reactions by further monomers or Polym ere can be coupled, known.
  • modified perfluorocarbons are prepared by oxidizing peroxygenated or plasma-chemically modified perfluoropolymers, which simultaneously have -COOH and / or -COF groups and reactive perfluoroalkyl (peroxy) radical centers, by substitution reactions and / or by addition reactions and / or reacted by free radical reactions with low molecular weight and / or oligomeric and / or polymeric substances and / or olefinically unsaturated monomers and / or olefinically unsaturated oligomers and / or olefinically unsaturated polymers.
  • aliphatic and / or aromatic and / or alkylaryl amino compounds such.
  • the object of the present invention is to provide modified perfluorocarbons which, processed in and / or on components, lead to improved sliding properties and wear resistance and thereby lead to a longer service life of the components and then at the same time improved hydrolytic stability and / or thermal stability and further to provide a simple and efficient method for producing such modified perfluorocarbons.
  • the modified perfluoroplastics according to the invention consist of perfluoropolymers and low molecular weight and / or oligomeric and / or polymeric compounds each having at least one hydroxyl group in the form of phenol groups and / or hydroxyaryl groups and / or hydroxyalkyl groups and / or polymer mixtures which have been chemically and / or plasma-chemically and / or thermomechanically modified at least one phenolic and at least one aliphatic hydroxy group on the aryl radical, which are reacted in a powder or paste or melt processing under shear conditions and the low molecular weight and / or oligomeric and / or polymeric di- and / or Polyhydroxyaryl compounds via ether bonds are chemically coupled to the perfluoropolymers.
  • PTFE (micro) powders are present as perfluoropolymers.
  • At least two hydroxy groups are present in the form of phenolic groups and / or hydroxyaryl groups and / or hydroxyalkyl groups.
  • polyether compounds from the class of polyglycols and / or polyester compounds and / or addition products of carboxylic acid and epoxides, which have at least one aliphatic and / or phenolic hydroxy group and / or further reactive-modifiable functional group, or mixtures thereof.
  • the PTFE is present as radiation-modified PTFE with at least 20 kGy, more advantageously at least 100 kGy, radiation-chemically modified PTFE.
  • modified perfluoropolymers are thermomechanically modified.
  • perfluoropolymers which are chemically and / or plasma-chemically and / or thermomechanically modified reactively and / or thermally reactivatable perfluoroalkyl (peroxy) radical centers and / or -COOH and / or COF groups and / or perfluoroalkylene Groups and / or thermally in situ activatable groups which cause the elimination of the formation of perfluorolefinic groups.
  • mixers and / or kneaders and / or twin-screw or multi-shaft extruders and / or planetary roller extruders are used to realize the shear conditions for the reactive reaction.
  • the reactive reaction takes place at temperatures of> 100 ° C. and preferably> 200 ° C.
  • the reactive reaction takes place at temperatures at least above or above the melt temperature of the PTFE material.
  • a further advantageous embodiment of the invention is that a further reactive reaction takes place after the reactive reaction.
  • the modified perfluoropolymer is used as a mixture of radiation-chemically and / or plasma-chemically and / or thermo-mechanically modified perfluoropolymers.
  • radiation-chemically and / or plasma-chemically and / or thermomechanically modified perfluoropolymers and low molecular weight and / or oligomeric and / or polymeric compounds having at least one hydroxyl group in the form of phenol groups and / or hydroxyaryl groups and / or hydroxyalkyl groups and / or at least one phenolic and at least one aliphatic hydroxyl group and reactively reacted in powder form or in paste form or in melt under shear conditions.
  • Radiation-chemically modified perfluoropolymer is advantageously used, wherein perfluoropolymer, which is chemically modified by oxygen exchange, is advantageously used.
  • a radiation-chemically modified PTFE is at least 20 kGy, more advantageously at least 100 kGy, radiation-chemically modified PTFE.
  • thermomechanically modified perfluoropolymer is used as the modified perfluoropolymer.
  • kneaders and / or twin- or multi-screw extruders and / or planetary roller extruders are used to realize the shear conditions for the reactive reaction.
  • the reactive reaction is carried out at temperatures of> 100 ° C and preferably> 200 ° C.
  • the reactive reaction is carried out at temperatures of at least or above the melt temperature of the PTFE material.
  • modified perfluoropolymer is used as a mixture of radiation-chemical and / or plasma-chemical and / or thermomechanically modified perfluoropolymers.
  • the modified perfluoropolymer in admixture with the low molecular weight and / or oligomeric and / or polymeric compound (s) having at least one hydroxy group in a kneader or (multi-shaft) extruder as a powder or paste mixture under shear Temperatures> 100 ° C, preferably> 200 ° C is processed.
  • the modified perfluoroplastics according to the invention and prepared according to the invention are used as additives in fats, oils or in bonded coatings, as additive / constituent in PF / phenol-formaldehyde and / or epoxy resins and other curable resins / polymer substances and / or in thermoplastics for tribologically stressed Form- / components and / or used as a reactive blend component and / or in substance for substrate surface modification or as a coating of components.
  • the radiation-modified and / or plasma-modified and / or thermomechanically modified perfluoropolymers with low molecular weight and / or oligomeric and / or polymeric compounds which are at least one Having hydroxy group in the form of phenol groups and / or hydroxyaryl groups and / or hydroxyalkyl groups and / or at least one phenolic and at least one aliphatic hydroxy group on the aryl radical, reacted reactively in a powder or paste or melt processing under shearing conditions by the hydroxy group or at least one of the hydroxy groups and preferably the phenolic hydroxyl group per molecule reacts with coupling to the perfluoropolymer.
  • the inventive via a hydrolysis-stable ether bond as a chemical bond between the perfluoropolymer particle surface and the low molecular weight and / or oligomeric and / or polymeric compounds, coupled, modified perfluorocarbons are realized.
  • hydroxyaryl is meant that in addition to at least one phenolic hydroxy group, at least one further reactive functional group and / or at least one further reactive modifiable center, such as in the phenol-formaldehyde resins, is present on the aryl radical.
  • radiation- and / or plasma-modified perfluoropolymers may possess carbonyl fluoride and / or carboxylic acid groups and persistent perfluoro (peroxy) radicals due to their preparation and modification. It is also known that carboxylic acid phenyl esters and also carboxylic acid alkyl esters are less resistant to hydrolysis, alcoholysis and / or amolysis and thereby react with cleavage of the (phenyl / alkyl) ester group.
  • a coupling of perfluoropolymers, and in particular of PTFE takes place only by reaction of a carbonyl fluoride group as activated carboxylic acid group on the PTFE with the phenol group to the phenyl ester.
  • a coupling of perfluoropolymers and in particular of PTFE by reaction of a carbonyl fluoride group as an activated carboxylic acid group on the PTFE with the hydroxyalkyl group to the alkyl ester take place.
  • modified perfluorocarbons are made of radiation-chemically and / or plasma-chemically and / or thermomechanically modified perfluoropolymers and low molecular weight and / or oligomeric and / or polymeric compounds having at least one hydroxy group in the form of phenolic groups and / or hydroxyaryl groups and / or hydroxyalkyl groups and / or at least one phenolic and at least one aliphatic hydroxy group on the aryl radical are formed by reactive reaction in a powder or paste or melt processing under shear conditions, of which the one or at least one of the phenol groups and / or hydroxyaryl groups and / or hydroxyalkyl groups per molecule to form a stable Ether bonding with the modified perfluoropolymer, and preferably with the PTFE, ie reacts with the PTFE particle surface, thereby achieving a stable chemical coupling.
  • the stable ether bonds formed according to the invention are formed either by substitution reactions of active and / or salt-activated phenol and / or hydroxyaryl and / or hydroxyalkyl groups with active and / or activated halogen groups or equivalent leaving groups or by a Michaelanaloge addition reaction of the phenolic and / or aliphatic hydroxy groups with existing and / or in situ formed / generated perfluorolefinic groups on the perfluoropolymer.
  • Perfluoroolefinic groups are present in the particle-chemical in low-concentration in the perennial and / or plasma-chemically modified perfluoropolymer and in particular PTFE. Such groups on the particle surface, accessible to agents, react because of the high reactivity e.g.
  • shielded active groups inside the particle can also be exposed by shearing, thus reacting with hydroxy groups to give ethers or thermally generated groups, e.g. produced by thermal decarboxylation reaction of the perfluoroalkylcarboxylic acid group and / or Dehydrohalogen michsre hope during the reactive reaction and reacted in situ with the hydroxyl groups of the phenol and / or hydroxyaryl and / or hydroxyalkyl compound.
  • modified perfluoroplastics according to the invention can be used as additives (for example for oils and greases as well as bonded coatings and / or in reactive resins such as phenolic resins, for example resole, epoxy resins, vinyl ester resins, UP resins (unsaturated Polyester resins) or other curable resins) and / or in substance, which are optionally / advantageously additionally modified with special adhesive / coupling groups such as phosphoric acid and / or phosphonic acid groups for fixing on substrate surfaces, such as metal surfaces, are used.
  • special adhesive / coupling groups such as phosphoric acid and / or phosphonic acid groups for fixing on substrate surfaces, such as metal surfaces, are used.
  • the chemical modification also results in a better dispersion due to the intensive interaction of the groups with the medium or the matrix.
  • the modified perfluoroplastics according to the invention can be incorporated / coupled into the matrix and / or can be compatibilized with the matrix only via the coupled radicals.
  • the chemically modified perfluoroplastics according to the invention can be used as primers in substance or in admixture with a further polymer substance for direct adhesion to material surfaces.
  • a significant advantage of this invention is that a chemically covalent, via ether bonds hydrolysis, alcoholysis and aminolysis and also thermally stable coupling of the perfluoropolymer particle with the low molecular weight and / or oligomeric and / or polymeric compounds is achieved.
  • modified perfluorinated plastics according to the invention can be covalently, ie chemically coupled / compatibilized, incorporated into phenol, melamine and urea resins and into epoxy resins and / or other curable resins in the subsequent reactions known to the person skilled in the art, thereby improving dispersion and thus improved material and tribological properties Properties can be achieved.
  • Example 1 The invention will be explained in more detail by several embodiments.
  • Example 1 The invention will be explained in more detail by several embodiments.
  • Example 1 The invention will be explained in more detail by several embodiments.
  • Example 1 The invention will be explained in more detail by several embodiments.
  • Example 1 Example 1 :
  • PTFE TF2025, emulsion polymer, Dyneon / 3M, 500 kGy, electron irradiated
  • novolak Bakelite PF 0205 DF 04
  • an electrically heated kneading chamber Haake laboratory kneader, 50 cc
  • 900 g of PTFE (Zonyl MP1 100, emulsion polymer, irradiated, DuPont) are premixed with 100 g of novolak (Bakelite PF 0205 DF 04) and slowly introduced into a Haake laboratory twin-screw extruder (16 mm, 100 rpm, temperature profile: 25 ° C - 250 ° C - 250 ° C - 200 ° C nozzle package 150 ° C) dosed.
  • the nozzle was previously removed from the nozzle pack so that the product reacted as a crumbly solid came out of the orifice and was collected in a vessel of liquid nitrogen.
  • the separation / extraction of the still soluble PF fractions was carried out as in Example 1.
  • the pink solid product ((PF + PTFE) -2, purified) has PF absorptions in the IR spectrum.
  • the follow-up operations as in Example 1 led to the same statement regarding hydrolysis, aminolysis, alcoholysis and thermal stability.
  • 900 g of PTFE (Zonyl MP1200, suspension polymer, irradiated, DuPont) are premixed with 100 g of novolak (Bakelite PF 0205 DF 04) and slowly poured into a Haake laboratory twin-screw extruder (16 mm, 100 rpm, temperature profile: 25 ° C.). 250 ° C - 250 ° C - 200 ° C - nozzle package without nozzle 150 ° C) dosed. The nozzle was removed from the nozzle pack so that the reactively reacted product came out of the aperture as a crumbly solid and was trapped in a vessel of liquid nitrogen. The separation / extraction of the still soluble PF fractions was carried out as in Example 1. The pink solid product has PF absorptions in the IR spectrum which were slightly lower than in Example 1. The
  • PTFE Zero g of PTFE (Zonyl MP1 100, emulsion polymer, irradiated, DuPont) are premixed with 5 g of DHDPSu and placed together in an electrically heated kneading chamber (Haake laboratory kneader, 50 cc) and reactively reacted at 250 ° C for 5 minutes at 100 rev / min , After opening the chamber, the product is removed.
  • kneading chamber Haake laboratory kneader, 50 cc
  • PTFE TF9205, Dyneon / 3M, thermomechanically modified, unirradiated
  • novolak Bakelite PF 0205 DF 04
  • an electrically heated kneading chamber Haake laboratory kneader, 50 cc
  • 270 ° C 5 Reactively reacted at 100 rpm for minutes After opening the chamber, the product is removed.
  • a PTFE-modified resol is obtained in which the PTFE is homogeneously dispersed and in which the modified PTFE particles only begin to sediment slowly after days.
  • Aramid fiber fleece is impregnated with the PTFE-modified resole, dried and pressed.
  • the pressed, cured plates have better mechanical and tribological properties than plates made with resole into which unmodified PTFE powder was stirred: + unmodified PTFE
  • thermosetting epoxy resin hardener: dicyandiamide
  • 10% by mass (PF + PTFE) -2
  • the particle size shows excellent dispersion stability during the curing process at 160 ° C. Sheets made from this material are sawn into test specimens and the tribological properties in the pad / ring test are investigated in comparison to pure epoxy resin and epoxy resin boards in which unmodified PTFE powder has only been physically dispersed.
  • the wear is 60% lower than for the sample with unmodified PTFE.
  • the pure epoxy resin without PTFE additive is not suitable for tribological applications in dry running / unlubricated.
  • Example 9 the epoxy resins modified with chemically modified perfluoroplastics, such as, for example, (PF + PTFE) -2, can also be further processed into fiber-reinforced materials and / or composites / composite materials.
  • PF + PTFE chemically modified perfluoroplastics
  • 25 g (PF + PTFE) -2 are dispersed in 200 ml NMP by means of an Ultraturraxrritter under inert gas / nitrogen purge.
  • 5 g of phosphorus pentoxide are added to the dispersion at 80 ° C. and the reaction system is heated to 150 ° C. with stirring and stirred for 2 hours. It is then heated to 190 ° C and after stirring for 30 minutes, the reaction was stopped. After cooling, 100 ml of water / methanol (1: 1) are added and stirred for 10 minutes. The dispersion is precipitated with stirring in methanol and filtered with suction.
  • the solid product is then stirred 3 times in water and filtered with suction, then heated in methanol for 1 hour under reflux and filtered off with suction and washed 2 times with methanol, filtered off with suction and dried. A pink PTFE powder was obtained.
  • the pink PTFE powder was applied to a steel plate and thermally baked at 330 ° C, resulting in a tight hydrophobic coating that is permanently water repellent and also not removable by rubbing or scratching.
  • 25 g (PF + PTFE) -1 are dispersed in 200 ml NMP by means of an Ultraturraxrritter under inert gas / nitrogen purge.
  • 5 ml of phosphoryl chloride are added at 80 ° C. and the reaction system is stirred for 2 hours. The mixture is then heated to 100 ° C and after stirring for 30 minutes, the reaction was stopped. After cooling, 100 ml of methanol are added and stirred for 10 minutes. The dispersion is precipitated with stirring in methanol and filtered with suction.
  • 25 g (PF + PTFE) -1 are dispersed in 200 ml NMP by means of an Ultraturraxrritter under inert gas / nitrogen purge.
  • 5 ml of phosphoryl chloride are added at 80 ° C. and the reaction system is stirred for 2 hours. The mixture is then heated to 100 ° C and after stirring for 30 minutes, the reaction was stopped. After cooling, 100 ml of water are added and stirred for 10 minutes. The dispersion is precipitated with stirring in methanol and filtered with suction.
  • PTFE Zero g of PTFE (Zonyl MP1 100, emulsion polymer, DuPont) are premixed with 25 g of polyethylene glycol (PEG: average molecular weight of 500 g / mol, a- / ⁇ x> -hydroxy-terminated) and mixed together in an electrically heated kneading chamber (Haake laboratory kneader, 50 cc) and reactively reacted at 250 ° C. for 5 minutes at 100 rpm. After opening the chamber, the product is removed.
  • PEG polyethylene glycol
  • PTFE tetrachloroethylene glycol
  • PEG average molecular weight of 550 g / mol, ⁇ -butoxy-Q-hydroxy terminated
  • PTF E Zonyl MP1 100, emulsion polymer, DuPont
  • PCI polycaprolactone
  • Vectra A 950 (LCP / liquid crystalline polyester: dried) are melted in an electrically heated kneading chamber (Haake laboratory kneader, 50 cc) and after setting a constant torque 20 g of PTFE (Zonyl MP1 100, emulsion polymer, DuPont) are added and at 280 ° C for 5 minutes reactively reacted at 100 rev / min. After opening the chamber, the product is removed.
  • PTFE Zeroyl MP1 100, emulsion polymer, DuPont
  • Lexan 141 polycarbonate / PC: dried
  • an electrically heated kneading chamber Haake laboratory kneader, 50 cc
  • 20 g of PTFE TF 2025, emulsion polymer, Dyneon / 3M, electron irradiated with 1000 kGy
  • the "ivory-like" product is removed.
  • PTFE TF 2025, emulsion polymer, Dyneon / 3M, gamma irradiated with 500 kGy
  • PP E powder 15 g
  • an electrically heated kneading chamber Haake laboratory kneader, 50 cc
  • This PPE + PTFE product was melt processed in the laboratory kneader with polystyrene in the ratio 80% PS and 20% PPE + PPE.

Abstract

L'invention s'applique au domaine de la chimie et concerne des plastiques perfluorés modifiés qui peuvent par exemple être utilisés comme vernis lubrifiants. L'objectif de la présente invention est de proposer des plastiques perfluorés modifiés qui conduisent à des propriétés de lubrification améliorées et à de meilleures résistances à l'abrasion. L'objectif est atteint par des plastiques perfluorés modifiés constitués par des polymères perfluorés modifiés et des composés de faible poids moléculaire et/ou oligomères et/ou polymères contenant chacun au moins un groupe hydroxy sous la forme de groupes phénol et/ou de groupes hydroxyaryle et/ou de groupes hydroxyalkyle et/ou d'au moins un groupe hydroxy phénolique et au moins un groupe hydroxy aliphatique sur le radical aryle, qui sont mis en réaction, les composés di- et/ou polyhydroxyaryliques de faible poids moléculaire et/ou oligomères et/ou polymères étant couplés chimiquement par des liaisons éther aux polymères perfluorés. L'objectif est également atteint par un procédé selon lequel des polymères perfluorés modifiés et des composés de faible poids moléculaire et/ou oligomères et/ou polymères sont homogénéisés et mis en réaction sous forme de poudre ou de pâte ou de masse fondue dans des conditions de cisaillement.
PCT/EP2011/062150 2010-07-22 2011-07-15 Plastiques perfluorés modifiés, leur procédé de fabrication et leur utilisation WO2012010515A1 (fr)

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DE102010038286A DE102010038286A1 (de) 2010-07-22 2010-07-22 Modifizierte Perfluor-Kunststoffe und Verfahren zu deren Herstellung und Verwendung
DE102010038286.8 2010-07-22

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